Process for producing linear polymers of alicyclic compounds

ABSTRACT

A process for producing linear polymers of alicyclic compounds comprising at least two double bonds by polymerizing them in the presence of a catalyst comprising pi -complexes of metals of group VI of the periodic system, as well as in the presence of compounds of said pi -complexes with acceptors of organic and acidoligands. Polymerization is carried out in the mass of a monomer or in a solution of hydrocarbons, halogen derivatives thereof or ethers. These catalysts enable the production of polymers with a high yield and at a good rate.

United States Patent Jufa et al.

[76] Inventors: Tatyana Lvovna Jufa, ulitsa Mayakovskogo, 3, kv. 23; Irina Alexandrovna Poletaeva, ulitsa l l l lntematsionala, 74, kv. 2l2; Vitaly Abramovich Kormer, ulitsa Zheleznovodskaya, 62, kv. 2; Boris Davydovich Babitsky, ulitsa Krasnogo Kursanta, 7, kv. 9; Mark losifovich Lobach, Annikov prospekt, 28, kv. 52; Viktoria Vladimirovna Markova, 2 Murinsky prospekt, 44, kv. 88; Lidia Alexandrovna Churlyaeva, ulitsa Avtovskaya, 2, kv. 147, all of, Leningrad, U.S.S.R.

221 Filed:' July 12, 1971 21 Appl.No.: 162,020

260/67 UA, 260/88.7 A, 260/9l.1 R, a 260/93.l, 260/93.5 R

" [11-1 1 3,821,181 [45'] June 28,1974

[51] Int. Cl. C08f 1/30 [58] Field of Search... 260/93.l, 93.5, 47 U, 67 UA,

260/88.7-A, 91.1 R, 91.5, 47 UA- Primary ExaminerStanford M. Levin Attorney, Agent, or Firm-Holman & Stern [57] ABSTRACT A process for producing linear polymers of alicyclic compounds comprising at least two double bonds by polymerizing them in the presence of a catalyst-comprising ir-complexes of metals of group VI of the peri- Odic'system, as well as in the presence of compounds Of said ii-complexes with acceptors of organic and acidoligands.-Polymerization is carried out in the mass of a'monomer or in a solution of hydrocarbons, halogen derivatives thereof or ethers.

These Catalysts enable the production. of polymers with a high yield and at a good rate.

8 Claims, No Drawings PROCESS FOR PRODUCING LINEAR POLYMERS F ALlCYCLllC COUNDS The present invention relates to processes for producing linear polymers of alicyclic compounds comprising at least two double bonds.

These polymers may be used as general-purpose rubbers in tire and vulcanized rubber production since they simulate alternating co-polymers of various olefins and dienes, the vulcanizates of said co-polymers having high physical characteristics and elasticity.

Known in the art is a process for producing polymers of alicyclic compounds comprising at least two double bonds, consisting in polymerizing said compounds with a ring opening in a solution or bulk in the presence of catalysts, comprising salts of chromium, molybdenum, tungsten and organo-metallic compounds of la, II and Illa groups of the periodic system.

The disadvantage of the prior art processes resides in the fact that the catalysts used are not sufficiently effective and stereospecific. Polymerization reactions which take place under the influence of these catalytic systems have substantial induction period in the'presence of a solvent and are accompanied by gelling. For this reason this process is scarcely suitable for commercial use.

It is an object of the present invention to provide a novel catalyst for a process of producing linear polymers of alicyclic compounds.

In accordance with the above and other objects of the invention the catalyst comprises 1r-complexesof metals of the group VI of the periodic system, as well as combinations of said complexes and acceptors of organic or acidoligands.

The most effective are catalysts comprising rr-allyl complexes of the general formula R1 R4 R1 a a (IF-OM41 MeXp (3- 5-40 MeXp in 1'1 in n in icfioq 111 wherein M represents Cr, Mo, W;

R, R R3, R, R are hydrogen, alkyl, cycloalkyl,

aryl. halogen;

X represents a monovalent anion selected from the group consisting of Cl, Br, I, CNS, OH, OAlk', CH COO, CCI COO, CF COO', N(Alk) C H OSO and These catalysts enable the production of polymers of alicyclic compounds with the highest yields.

It is also advantageous to use 1r-complexes of the general formula,

wherein Me represents Cr, Mo, W;

L represents a ligand selected from the group consistll'lg Of CO, C5H5, C7Hg, CGHG, CgHg, PCI3, PR3, )a;

R represents an organic radical; and

1r-complexes such as cyclopentadienylcarbonyl, cy-

clooctadienecarbonyl, cycloheptatrienecarbonyl, arenecarbonyl, cyclooctatetraenecarbonyl, norbornenecarbonyl, cyclododecatrienecarbonyl, trichlorphosphinecarbonyl, triphenylphosphinecarbonyl,

orphosphinecyclooctadiene,

triphenylphosphitecarbonyl, cyclopentadienecyclooctadiene, arenecyclopentadiene, cyclopentadienylcycloheptatriene, norbornenecyclopentadiene, cyclooctatetraencyclopentadiene, cyclopentadienylcyclododecatriene, trichlorophosphinecyclopentadienyl, triphenylphosphitecyclopentadienyl, arenecyclooctadiene, cycloheptatrienecyclooctadiene, norborenecyclooctadiene, cyclooctatetraenecyclooctadiene, trichltriphenylphosphinecyclooctadiene, triphenylphosphitecyclooctadiene, arenecyclododecatriene, arenecycloheptatriene, arenenorbornene, arenecyclooctatetraene, arenetrichlorophosphine, arenetriphenylphosphite, trichlorphosphinecyclododecatriene, trichlorophosphinebornene, trichlorphosphinecycloheptatriene, trichlorophosphinecyclododecatriene, triphenylphosphinecyclododecatriene, triphenylphosphinecyclododecatriene, triphenylphosphinenorbornene, triphenylphosphinecycloheptatriene, triphenylphosphitenorbornene, triphenylphosphitecycloheptatriene complexes of metals of the group Vl may be used.

As acceptors of organic and acidoligands compounds of the general formula, MZn, wherein M represents metals of groups llI-VIll of the periodic system; Z represents a halogen atom, alkyl, aryl, as well as combinations thereof; and n 2-6 may be used.

As monomers substituted and unsubstituted alicyclic compounds comprising at least two double bonds are used.

Substitutes for hydrogen in the ring may comprise alkyl-, aryl-, aralkyl-, alkaryl-, acyl-, alkoxy-, cyano-, carbalkoxy-, aryloxy-, acyloxy-, aroyloxy-groups and halogen atoms. The ring of the alicyclic compound may comprise one or several such groups and atoms.

Polymerization of alicyclic compounds in the presence of the above-mentioned catalysts may be performed in hydrocarbons, halohydrocarbons and ethers.

The present process for producing linear polymers of alicyclic compounds is carried out as follows:

An alicyclic compound is polymerized for 01-20 hours in the presence of small quantities of the abovementioned catalyst at a temperature of from -50"C to +C. Polymerization may take place both in the above-mentioned solvents and without them, that is, in the bulk of the monomer. The catalyst may be prepared either in the presence or absence of a monomer.

The molar ratio between an acceptor of organic and acidoligands and a rr-complex is selected within the range of from 0.5 to l0:l, and preferably of from 2:1 to 6:1.

The molar ratio between a monomer and a 'rr-complex may be selected within the range of from 50:1 to 10,000: 1, and preferably of from 300:1 to 3,000zl.

The polymer which is thus produced is isolated from the solution by any conventional method, such as by adding alcohol or evaporating the solvent.

The isolated polymer is used in preparation of rubber mixtures and vulcanizates.

The invention permits the polymerization of alicyclic compounds comprising at least two double bonds with a ring opening more efficiently than with prior art catalysts. Polymerization of the above-said alicyclic compounds in the presence of the catalysts according to the present invention is performed at good rates even utilizing small quantities of the'catalyst. Polymerization 3 takes place without gelling and is commercial quite useful.

The present invention will be better understood from the following illustrative examples of producing linear polymers of alicyclic compounds.

Example 1 v Benzene solutions of aluminium bromide (2.10 mole) and tetra(rr-crotyl)tungsten (1.10" mole were poured into'a 100 ml glass ampoule. Then 8.9 g of trans, trans, cis-cyclododecatriene-l,5,9 were added. Polymerization was performed at 30C over hours. The polymer yield was of 8.1 g (91% of the theoretical amount). The polymer contained 60% of transand 40% of cis-double bonds. lntrinsic viscosity of the polymer (1;) 1.54 dl/g (in benzene at 25C).

Example 2 Benzene solutions of gallium bromide (6.10 mole) and tungsten hexacarbonyl (3.10 mole) were poured into a 100 ml glass ampoule. Then 13.2 g of cyclooctadiene were added. Polymerization was performed at 30C over hours. The polymeryield was of 5.9 g (45% of the theoretical amount). The polymer contained 40% of cisand 60% of trans-double bonds. Intrinsic viscosity of the polymer (1 2.25 dl/g (in benzene at 25C).

Example 3 Benzene solutions of ethylaluminium dichloride (8.10' mole) and tetra('rr-allyl)molybdenum (4.10

mole) were poured into a 100 ml glass ampoule. Then 15.2 g of l-chlorcyclooctadiene-l,5 was added. Polymerization was performed at 30C over 16 hours. The polymer yield was of 9.1 g (60% of the theoretical amount). The polymer contained 30% of transand 70% of cis-double bonds. Intrinsic viscosity of the polymer ('n) 1.65 dl/g (in benzene at 25C).

Example 4 Benzene solutions of tetrabutyltin (8.10" mole) and tris(1r-crotyl)tungsten chloride (4.10" mole) were poured into a 100 m1 ampoule. Then 12.2 g of l-methylcyclooctadiene-l,5 was added. Polymerization was performed at 30C over 6 hours. The polymer yield was of 11.6 g (95% of theoretical amount). The polymer contained 40% of transand 60% of cis-double bonds. Intrinsic viscosity of the polymer (n) 0.63 dl/g (in benzene at 25C).

Example 5 Benzene solutions of tris(1r-ally)tungsten trifluoracetate (1.10" mole) and 8.9 gof trans, trans, ciscyclododecatriene-l.5,9 were poured into a 100 ml glass ampoule. Polymerization was performed at 30C over hours. The polymer yield was of 2.7 g (30% of the theoretical amount). The polymer contained 55% of transand of cis-double bonds. Intrinsic viscosity of the polymer (17) 1.20 dl/g (in benzene at C).

Example 6 Solutions of tungsten hexachloride (8.10 mole) and tris(1r-allyl)tungsten iodide (2.10" mole) in hexane were poured into a 100 ml glass ampoule. Then 22.7 g of 5-ph-enycycloundecadienel ,6 were added. Polymerization was performed at C during 3 hours. The polymer yield was of 17 g (75% of the theoretical amount). The polymer contained 40% of trans and of cis-double bonds. Intrinsic viscosity of the polymer (1 1.6 dl/g (in benzene at 25C).

Example 7 Solutions of diethyl aluminium chloride (6.10 mole) and benzene molybdentricarbonyl (2.10 mole) in diethyl ether were poured into a 100 ml glass ampoule. The l l g of cyclooctadienel ,5 was added. Polymerization was perfonned at 20C during 10 hours. The polymer yield was of 2.8 g (25 of the theoretical amount). The polymer contained 45% of transand 5 5% of cis-double bonds. Intrinsic viscosity of the polymer (17) 2.2.dl/g (in'benzene at 25C).

Example 8 Solutions of aluminium bromide (4.10 mole) and tris(1T-allyl)methoxytungsten (2.10' mole) in chlorobenzene were poured into a 100 ml glass ampoule. Then 16 g of trans-, trans-, cis-cyclododecatriene-l ,5,9 were added. Polymerization was performed at 0C over 1 hour. The polymer yield was of 14.2 g (89% of the theoretical amount). The polymer contained 60% of transand 40% of cis-double bonds. Intrinsic viscosity of the polymer (1 1.70 dl/g (in benzene at 25C).

Thus, referring to the above examples, polymerization of alicyclic compounds comprising at least two double bonds in the presence of 'rr-complexes of metals of group VI of the periodic system and combinations thereof with acceptors of organic and acidoligands takes place at a good rate and requires small catalyst consumption. As distinguished from the processes carried out in the presence of prior art catalysts of the Ziegler-Nutt type, the catalysts according to the present invention, being characterized by substantially higher efficiency and stereospecificity, enable polymerization in the presence of a solvent without an induction period. Polymerization is not accompanied by gelling. These considerations show that the process according to the invention is more suitable for the development of a commercial-scale process.

What is claimed is:

l. A process for producing linear polymers of unsaturated alicyclic compounds containing from 8 to 12 carbon atoms in the cyclic ring and containing from 2 to 3 unconjugated double bonds in the cyclic ring, comprising polymerizing one of said compounds at a temperature within the range of from about 50C to about +C in the presence of a catalyst selected from the group consisting of rr-complexes of the general formula and [Me (L)n ]m and combinations of said rr-complexes with acceptors of organic and acidoligands,

wherein Me represents a metal selected from the group consisting of Cr, Mo and W;

R, R R, R, R are selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl and halo- X represents a monovalent anion selected from the group consisting of Cl, Br, 1', CNS, OH,

L represents a ligand selected from the group consisting of CO,C5H5, C7H8, C5H6, CBHS, PCla, PR3, P(OR) and combinations thereof;

R represents an organic radical;

n? 14; n 26; m =1-2;p 0-3; and q =1-9; the molar ratio between said alicyclic compound and wherein Me represents a metal selected from the group consisting of Cr, Mo and W;

R, R R, R, R are selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl and halo- X represents a monovalent anion selected from the group consisting of Cl, Br, I, CNS, OH, OAlk', CH COO, CCl COO, CF COO N(Al- 92 d, s s 2 and n l-4; M l-2; p 0-3; and q l-9.

4. A process according to claim I wherein said 1r-complexes comprise rr-complexes of the general formula a-Jlnln 1m 7 wherein Me represents a metal selected from the group consisting of Cr, Mo and W;

L represents a ligand selected from the group consisting of CO, C H C H C 11 C H PCl PR P(OR) and combinations thereof;

n 26; and m l-2; and

R represents an organic radical.

5. A process according to claim I, wherein said acceptors of organic and acidoligands comprise compounds of the general formula, MZn, wherein M represents a metal of groups Ill-VIII of the periodic system; Z is selected from the group consisting of halogen atoms, alkyl, aryl, and combinations thereof; and n 2-6.

6. A process according to claim l, wherein the molar ratio between an acceptor of organic and acidoligands and a rr-complex is within the range of from 2:1 to 6:1.

thereof and ethers.

v UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENT NO. 3,821, 181 DATED June 28, 1974 'NVENTOWS) I TATYANA L; JUFA, ET AL it is certified that error appearsin the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 1. line 40,

I x p or c-- MeXp 2 '3 I 5 R R P. n m (CH3) n m should read 2 2 q or 2 2 R2 1?;1 MeXP c ;c;- ;c 'Mexp R3 R5 n m (CH4 n m 3 q Column 1, line 49, "N(Alk) should read -N(Alk);-

Column 1., line 63, "cyclopentadienylcarbonyl" should read -cyclopentadienecarbonyl- Column 2, line 3, "cyclopentadienylcy-" v cyclopentadienecy Column 2, line 4, "cyclopentadienylcy-" should read -cyclopentadienecy- Column 2, line 5, "trichlorophosphinecyclopentadienyl" should read --trich1.orophosphinecyclopentadiene Colum 2, line 6, "triphenylphosphitecyclopentadienyl" should read --triphenylphosphitecyclopentadiene-- Column 2, line 14, "trichlorophosphenebor" should read --trichlorophosphenenorborshould read UNITED STATES PATENT OFFICE g CERTIFICATE OF CORRECTION PATENT NO. 1 3,821., 181 DATED June 2 3, 1974 INVENTOWS) 1 'I'A'I'YANA L. JUFA, ET AL It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 2, line 17, cancel "triphenylphosphinecyclododeca-" Column 2, line 18, cancel "triene" Column 4, line 4, 25" should read -25';--

column 4, line 47,

cc|-c Mexp c\--T7 MeXp R2 R3 L5 n m (CH2) n m should read r q r r 1 r R2 r T c.- ;T =c MeXp or Ci; 7c MeXp 1'2 R3 2L n m (ca n m Column 5, line 9, "arylkyl" should read --aralkyl- Column 5, line 17,

C ===T Mexp should read 2 3 1'? R R [n] n m l 4 7 r r C: :C: :.C MeKp L i 19 L n m UNITED STATES PATENT OFFICE 98 CERTIFICATE OF CORRECTION PATENT NO. 3,821,181 DATED June 28, 1974 INVENTOR(S) I TATYANA L. JUFA, ET AL it is certified that error appears in the above-identified patent and that said LettersPatent are hereby corrected as shown below:

Column 5, line 23, I 1& R

$ Meip l 1 should {CH n] n .m

read R *2 i b: -'.C:.7 Me zit) H2) n m C. MARSHALL DZQTN Commissioner of Patents and Trademarks RUTII C. EfASON Attesting Officer 

2. A process according to claim 1, wherein said alicyclic compounds have substituted for hydrogen atoms in the ring substituents selected from the group consisting of alkyl-, aryl-, arylkyl-, alkaryl-, acyl-, alkoxy-, cyano-, carbalkoxy-, aryloxy-, acyloxy-, aroyloxy- groups and halogen.
 3. A process according to claim 1 wherein said pi -complexes comprise pi -allyl compounds of the geNeral formula
 4. A process according to claim 1 wherein said pi -complexes comprise pi -complexes of the general formula ((Me(L) n n )m wherein Me represents a metal selected from the group consisting of Cr, Mo and W; L represents a ligand selected from the group consisting of CO, C5H5, C7H8, C6H6, C8H8, PCl3, PR3, P(OR)3 and combinations thereof; n2 2-6; and m 1-2; and R represents an organic radical.
 5. A process according to claim 1, wherein said acceptors of organic and acidoligands comprise compounds of the general formula, MZn, wherein M represents a metal of groups III-VIII of the periodic system; Z is selected from the group consisting of halogen atoms, alkyl, aryl, and combinations thereof; and n 2-6.
 6. A process according to claim 1, wherein the molar ratio between an acceptor of organic and acidoligands and a pi -complex is within the range of from 2:1 to 6:1.
 7. A process according to claim 1, wherein the molar ratio between an alicyclic compound and a pi -complex is within the range of from 300:1 to 3,000:1.
 8. A process according to claim 1 wherein polymerization is carried out in the bulk of a monomer or in a solvent selected from the group consisting of aromatic, aliphatic, alicyclic hydrocarbons, halogen derivatives thereof and ethers. 